CN115261564A - Non-aluminum deoxidation raw material pure iron for amorphous soft magnetic thin strip and preparation method thereof - Google Patents
Non-aluminum deoxidation raw material pure iron for amorphous soft magnetic thin strip and preparation method thereof Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 182
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 88
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 41
- 239000002994 raw material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000010959 steel Substances 0.000 claims abstract description 95
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 94
- 238000000034 method Methods 0.000 claims abstract description 54
- 239000002893 slag Substances 0.000 claims abstract description 44
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000007670 refining Methods 0.000 claims abstract description 21
- 238000005261 decarburization Methods 0.000 claims abstract description 20
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 16
- 230000023556 desulfurization Effects 0.000 claims abstract description 16
- 238000003723 Smelting Methods 0.000 claims abstract description 14
- 238000010079 rubber tapping Methods 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 32
- 238000009749 continuous casting Methods 0.000 claims description 25
- 229910052698 phosphorus Inorganic materials 0.000 claims description 23
- 238000005266 casting Methods 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 12
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 12
- 239000004571 lime Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 229910052748 manganese Inorganic materials 0.000 claims description 11
- 230000000903 blocking effect Effects 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 229910000514 dolomite Inorganic materials 0.000 claims description 6
- 239000010459 dolomite Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910001209 Low-carbon steel Inorganic materials 0.000 claims description 5
- 238000007664 blowing Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 claims description 5
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 239000003595 mist Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 241001062472 Stokellia anisodon Species 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052791 calcium Inorganic materials 0.000 abstract description 8
- 239000011575 calcium Substances 0.000 abstract description 8
- 229910000519 Ferrosilicon Inorganic materials 0.000 abstract description 4
- 238000009851 ferrous metallurgy Methods 0.000 abstract description 2
- 239000011572 manganese Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 16
- 239000010936 titanium Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 3
- 239000005997 Calcium carbide Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/10—Handling in a vacuum
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/0006—Adding metallic additives
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/06—Deoxidising, e.g. killing
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/064—Dephosphorising; Desulfurising
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/072—Treatment with gases
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/076—Use of slags or fluxes as treating agents
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Treatment Of Steel In Its Molten State (AREA)
Abstract
The invention belongs to the technical field of ferrous metallurgy, and particularly relates to non-aluminum deoxidation raw material pure iron for an amorphous soft magnetic ribbon and a preparation method thereofThe method is carried out. Performing pretreatment desulfurization and demanganization on molten iron to obtain low-S and low-Mn molten iron; the converter is filled with full molten iron, so that impurities brought by scrap steel are avoided; the smelting process adopts a double slag method to carry out deep demanganization and dephosphorization; the converter tapping and refining process does not perform deoxidation operation on molten steel and slag, and molten steel [ O ] is maintained]Content, further demanganizing and dephosphorizing; utilization of original [ O ] in molten Steel in RH Process]The decarburization reaction is carried out spontaneously under high vacuum degree, and the molten steel is deoxidized by adopting high-purity ferrosilicon to replace aluminum after the decarburization is finished, so that the generation of Al is avoided2O3The inclusion improves the purity of the molten steel, and meanwhile, good castability can be obtained without calcium treatment. The method can prepare the non-aluminum deoxidation raw material pure iron which completely meets the requirements of the amorphous soft magnetic thin strip.
Description
Technical Field
The invention belongs to the technical field of ferrous metallurgy, and particularly relates to non-aluminum deoxidation raw material pure iron for an amorphous soft magnetic ribbon and a preparation method thereof.
Background
The raw material pure iron is one of pure iron, the lower the content of other elements except Fe in steel is, the better, the pure iron is usually used for preparing amorphous and nanocrystalline soft magnetic thin strips and is a typical high-technology value-added product. When preparing the amorphous soft magnetic ribbon, the raw material pure iron is melted, and then other elements such as Si, co, ni and the like are added to obtain a mixed molten metal liquid, and then the mixed molten metal liquid is directly sprayed onto a cooling carrier through a nozzle by a strip throwing method, so that the molten steel is rapidly solidified into the ribbon with a certain thickness.
The contents of P, S, al and Ti elements and Al in the raw material pure iron2O3The inclusions can cause nozzle blockage or melt spinning fracture in the preparation process, and elements such as C, mn, O and the like can greatly reduce the soft magnetic performance of the material, so that the lower the elements such as C, mn, P, S, al, ti and O, the better the raw material pure iron for preparing the amorphous soft magnetic thin strip is. Aluminum is one of important molten steel deoxidizing materials in the steelmaking process, and the adoption of aluminum for deoxidizing molten steel can ensure good molten steel deoxidization, but can not avoid Al generation in the deoxidization process2O3Inclusions and a certain aluminum content of the molten steel remain, which is extremely harmful to the preparation of amorphous soft magnetic thin strip. Therefore, the content of elements such as aluminum and the like and Al are reduced as much as possible under the condition of ensuring good deoxidation of molten steel2O3Impurities and improves the purity of the raw material pure iron, which is a technical problem in the field of raw material pure iron production in the steel industry.
Disclosure of Invention
The invention aims to provide non-aluminum deoxidation raw material pure iron for an amorphous soft magnetic thin strip and a production method thereof. The non-aluminum deoxidation raw material pure iron for the amorphous soft magnetic thin strip comprises the following components in percentage by mass: less than or equal to 0.005%, si: less than or equal to 1.0 percent, mn: less than or equal to 0.06%, P: less than or equal to 0.015%, S: less than or equal to 0.010 percent, less than or equal to 0.005 percent of Al, less than or equal to 0.004 percent of Ti, less than or equal to 0.004 percent of N, less than or equal to 0.007 percent of T [ O ], and the balance of Fe and inevitable impurities;
the optimized chemical components and weight percentage content of the non-aluminum deoxidation raw material pure iron for the amorphous soft magnetic ribbon are as follows: c: less than or equal to 0.002%, mn: less than or equal to 0.05 percent, si:0.65 to 0.85%, P: less than or equal to 0.010 percent, S: not more than 0.008 percent, not more than 0.003 percent of Al, not more than 0.002 percent of Ti, N: less than or equal to 0.003 percent, less than or equal to 0.005 percent of T [ O ], and the balance of Fe and inevitable impurities.
The preparation method of non-aluminum deoxidation raw material pure iron for the amorphous soft magnetic ribbon comprises the following process routes: KR pretreatment of molten iron, smelting in a converter, LF treatment, RH decarburization treatment, deoxidation treatment and continuous casting of small square billets; the KR pretreatment of the molten iron is divided into two steps, and desulfurization and demanganization operations are respectively carried out to reduce the contents of manganese and sulfur in the molten iron entering the furnace; charging the molten iron into a converter for smelting, so as to avoid impurity elements brought by scrap steel; a double-slag method is adopted for converter smelting, and the demanganization and dephosphorization rates are enhanced; and (3) controlling the composition of the converter end point: less than or equal to 0.06 percent of C, less than or equal to 0.05 percent of Mn, less than or equal to 0.010 percent of P, less than or equal to 0.006 percent of S, less than or equal to 0.002 percent of Ti; after tapping, a slag stopping plug and a sliding plate are used for stopping slag to avoid slag discharging and rephosphorization; the deoxidation operation is not carried out on the molten steel and the slag in the tapping and refining processes of the converter, the elements such as manganese, phosphorus, titanium and the like in the molten steel can be further removed, the Mn is less than or equal to 0.04 percent, the P is less than or equal to 0.008 percent, the Ti is less than or equal to 0.001 percent after the refining is finished, and the molten steel [ O ] is]The content is controlled to be 600-900 ppm; oxygen blowing is not carried out in the RH process, and only the original [ O ] in the molten steel is utilized]Under high vacuum, the carbon-oxygen reaction is carried out spontaneously to remove the carbon content to be within 0.002 percent and to obtain the product [ O ]]The content is 400-600 ppm; after RH decarburization, high-purity ferrosilicon is adopted to replace aluminum for deoxidation operation, and molten steel [ O ]]The content is less than or equal to 50ppm, the Al content is less than or equal to 0.003 percent, and the generation of Al is avoided2O3Class of foreign matter, and passMost of deoxidation products are removed by RH circulation; by adopting a non-aluminum deoxidation mode, the molten steel casting process still has good castability under the condition of avoiding calcium treatment operation on the molten steel; the continuous casting is small square billet continuous casting with the section of 160mm multiplied by 160mm, the drawing speed is 2.0 m/min-2.3 m/min, and the low-power shrinkage cavity of the casting billet can be controlled to be not more than 0.5 grade by matching with the light-weight reduction with the total reduction of 16 mm.
The method comprises the following steps of:
1) Molten iron KR pretreatment desulfurization demanganization
Selecting molten iron with Si less than or equal to 0.40 percent, mn less than or equal to 0.40 percent and P less than or equal to 0.150 percent to carry out KR pretreatment, and carrying out the KR pretreatment by two steps: firstly, 6-9 kg/t of high-quality active lime (the CaO content is more than or equal to 85 percent, the activity degree is more than or equal to 260 percent) is added into a molten iron tank and stirred for 10-15 min for desulfurization treatment, slag is removed, and the S content of the desulfurized molten iron can be reduced to be within 0.002 percent; and secondly, continuously adding 8-15 kg/t of iron scale into the molten iron tank, stirring for 15-20 min at the stirring speed of 40-60 r/min, performing demanganization treatment, removing slag, and controlling the Mn content of the demanganized molten iron to be within 0.25%.
2) Converter full molten iron charging double slag method for smelting demanganization and dephosphorization
The molten iron raw material in the step 1) is used for charging the molten iron, and no scrap steel is charged, so that the scrap steel is prevented from being brought into impurity elements such as P, S and the like; the converter adopts a double-slag method for smelting, the adding amount of active lime is 38-48 kg/t, the adding amount of light-burned dolomite is 8-12 kg/t, the adding amount of raw dolomite is 10-20 kg/t, the adding amount of ore is 20-30 kg/t, the oxygen supply time is 15-18 min, and the oxygen supply amount is 7000m3～9000m3(ii) a Controlling the end point temperature to be 1580-1620 ℃, and controlling the end point components: less than or equal to 0.06 percent of C, less than or equal to 0.05 percent of Mn, less than or equal to 0.010 percent of P, less than or equal to 0.006 percent of S, less than or equal to 0.002 percent of Ti, and [ O ] in molten steel]The content is 500ppm to 800ppm; tapping time is 4-6 min; deoxidizing operation is carried out without adding a deoxidizing agent in the tapping process, and only 4-6 kg/t of high-quality active lime (the CaO content is more than or equal to 85 percent, and the activity is more than or equal to 260 percent) is added as top slag; and in the later tapping stage, slag blocking operation is performed by adopting a slag blocking plug and a sliding plate for slag blocking, so that slagging and rephosphorization are avoided.
3) Refining without deoxidation treatment
Step 2), electrifying and heating the molten steel to a refining station for 30-40 min; deoxidizing agents such as calcium carbide, aluminum particles and the like are not added in the refining process to deoxidize the slag and the molten steel, and elements such as Mn, P, ti and the like in the molten steel are further removed, so that the Mn at the refining end point is less than or equal to 0.04%, the P is less than or equal to 0.008%, the Ti is less than or equal to 0.001%, and the [ O ] content of the molten steel is controlled at 600-900 ppm; the refining is finished when the temperature of the molten steel reaches more than 1650 ℃.
4) RH circulation decarburization treatment
After the molten steel in the step 3) arrives at an RH station, oxygen blowing operation is not carried out, circulation is carried out under the vacuum degree of less than or equal to 133Pa, argon is adopted as lifting gas, the flow rate is 100-120 Nm3H, make original [ O ] in molten steel]Carrying out carbon-oxygen reaction with element C for decarburization treatment; after circulating for 3-8 min, the content of C in molten steel can be reduced to be within 0.002%, and the molten steel [ O ]]The content is 400ppm to 600ppm.
5) Silicon deoxidation treatment of molten steel
Step 4) after the decarburization treatment of the molten steel is finished, continuously maintaining the vacuum degree of less than or equal to 133Pa at an RH station, adding 10-15 kg/t of high-purity silicon iron (the contents of P, S, al and Ti elements do not exceed 0.02%) to replace aluminum for deoxidation treatment, wherein the Si content of the molten steel is 0.65-0.85%, the Al content is less than or equal to 0.003%, and the [ O ] content is less than or equal to 50ppm after the deoxidation; and continuously circulating for 5-10 min after the deoxidation is finished, finishing the vacuum, and adding a low-carbon steel coating agent (the carbon content is less than or equal to 2%) on the surface of the molten steel.
6) Light and heavy reduction of continuous casting of small square billet
Casting in a small square billet continuous casting machine with the section of 160mm multiplied by 160 mm; in the continuous casting process, a low-carbon tundish covering agent (the carbon content is less than or equal to 2%) and ultra-low carbon protective slag (the carbon content is less than or equal to 8%) are used; the superheat degree of the molten steel is 30-45 ℃, the continuous casting drawing speed is 2.0-2.3 m/min, and secondary cooling is carried out by adopting aerial fog; the straightening temperature of the casting blank is 1000-1200 ℃; after straightening a casting blank, carrying out three-roll light-heavy reduction with total reduction of 16mm at the position with the solid phase rate of 50-100%, wherein the total reduction of the first two rolls is 8mm, and the reduction of the third roll is 8mm; after the light and heavy reduction is carried out, the low-power shrinkage cavity of the casting blank can be controlled within 0.5 grade.
The invention has the beneficial technical effects that:
by the preparation method, molten iron is pretreated by KR desulfurization and demanganizationIn principle, the converter adopts full molten iron to be filled for double-slag smelting, refining non-deoxidation treatment and RH circulation decarburization treatment, so that the components of the molten steel can be controlled as follows: less than or equal to 0.002 percent of C, less than or equal to 0.05 percent of Mn, less than or equal to 0.010 percent of P, less than or equal to 0.008 percent of S, less than or equal to 0.003 percent of Al and less than or equal to 0.002 percent of Ti; the molten steel after RH decarbonization is deoxidized by using high-purity ferrosilicon instead of aluminum to remove T [ O ]]The content is controlled to be not more than 0.005%, and the Al content is controlled to be not more than 0.003% in an ultralow range, so that the Al generated in the deoxidation process is avoided2O3The impurities improve the purity of the molten steel and solve the technical problem of producing the raw material pure iron for the amorphous soft magnetic thin strip.
According to the invention, the Mn content of the components of the molten iron entering the furnace can be effectively controlled by performing the demanganization pretreatment on the molten iron, the auxiliary material consumption and smelting time of the follow-up converter double-slag demanganization can be effectively reduced, and the metal yield is improved; and the iron scale is common waste in steel plants, so that the method for recycling and comprehensively utilizing the iron scale is indirectly provided, and has certain significance of low carbon, environmental protection, energy conservation and consumption reduction.
Description of the drawings:
FIG. 1 example 1 (using light and heavy reduction) is a low magnification photograph of a cross section of a continuous casting slab;
FIG. 2 is a longitudinal low magnification photograph of a continuous cast slab in example 1 (under light and heavy reduction);
FIG. 3 is a low magnification photograph of a cross section of a continuous casting slab in comparative example 3 (no light and heavy reduction is used);
FIG. 4 is a longitudinal low magnification photograph of a continuous cast slab of comparative example 3 (no light and heavy reduction is used).
Detailed Description
The present invention will be described in detail with reference to examples. The following examples are merely illustrative of the best mode of carrying out the invention and do not limit the scope of the invention in any way.
Example 1
1) Molten iron KR pretreatment desulfurization demanganization
Molten iron with 0.20 percent of Si, 0.33 percent of Mn, 0.107 percent of P and 0.030 percent of S is selected for KR pretreatment and is carried out by two steps: firstly, adding 7kg/t of high-quality active lime into a molten iron tank, stirring for 10min, performing desulfurization treatment, removing slag, and reducing the S content of the desulfurized molten iron to 0.001%; and secondly, continuously adding 13kg/t of iron scale into the molten iron tank, stirring for 18min, performing demanganization treatment, removing slag, and controlling the Mn content of the demanganized molten iron to be 0.225%.
2) Converter full molten iron charging double slag method for smelting demanganization and dephosphorization
The molten iron raw material in the step 1) is used for charging the molten iron, no scrap steel is charged, the charging amount is 135t, and the scrap steel is prevented from being brought into impurity elements such as P, S; the converter adopts a double-slag method for smelting, the adding amount of active lime is 39kg/t, the adding amount of light-burned dolomite is 9kg/t, the adding amount of raw dolomite is 12kg/t, the adding amount of ore is 25kg/t, the oxygen supply time is 16min, and the oxygen supply amount is 8147m3(ii) a End point temperature control 1618 ℃, end point composition control: 0.048 percent of C, 0.009 percent of Si, 0.047 percent of Mn, 0.009 percent of P, 0.006 percent of S, 0.002 percent of Ti and [ O ] in molten steel]Content 652ppm; tapping time is 4min; deoxidizing operation is carried out without adding a deoxidizing agent in the tapping process, and only 5kg/t of high-quality active lime is added as top slag; and in the later tapping stage, slag blocking operation is performed by adopting a slag blocking plug and a sliding plate for slag blocking, so that slagging and rephosphorization are avoided.
3) Refining non-deoxidation treatment
Step 2) carrying out electrifying and heating treatment on the molten steel after the molten steel reaches a refining station, wherein the treatment time is 35min; deoxidizing agents such as calcium carbide, aluminum particles and the like are not added in the refining process to perform deoxidation operation on the slag and the molten steel, and elements such as Mn, P, ti and the like in the molten steel are further removed, so that the refining end point C is 0.037%, si is 0.003%, mn is 0.028%, P is 0.004%, S is 0.005%, ti is 0.0002%, and the [ O ] content of the molten steel is controlled at 792ppm; finishing refining when the temperature of the molten steel reaches 1680 ℃.
4) RH circulation decarburization treatment
After the molten steel reaches the RH station in the step 3), oxygen blowing operation is not carried out, circulation is carried out under the vacuum degree of 103Pa, argon is used as lifting gas, and the flow rate is 120Nm3H, make original [ O ] in molten steel]Carrying out carbon-oxygen reaction with element C for decarburization treatment; after circulating for 4min, the content of C in molten steel can be reduced to 0.002%, and the content of [ O ] in molten steel]The content was 492ppm.
5) Silicon deoxidation treatment of molten steel
Step 4) after the decarburization treatment of the molten steel, continuously maintaining the vacuum degree of 103Pa at an RH station, adding 14kg/t of high-purity silicon iron (the contents of P, S, al and Ti elements do not exceed 0.02%) to replace aluminum for deoxidation treatment, wherein the content of Si in the molten steel after deoxidation is 0.002%, the content of Al is 0.001%, and the content of [ O ] is less than or equal to 50ppm; and (3) after the deoxidation is finished, continuously circulating for 10min, finishing the vacuum, and adding a low-carbon steel coating agent (the carbon content is less than or equal to 2%) on the surface of the molten steel.
6) Light and heavy reduction of continuous casting of small square billet
Casting in a small square billet continuous casting machine with the section of 160mm multiplied by 160 mm; a low-carbon tundish covering agent (the carbon content is less than or equal to 2%) and ultra-low carbon protective slag (the carbon content is less than or equal to 8%) are used in the continuous casting process; the superheat degree of the molten steel is 32 ℃, the continuous casting drawing speed is 2.3m/min, and secondary cooling is carried out by adopting gas mist; the straightening temperature of the casting blank is 1150 ℃; after straightening a casting blank, carrying out three-roll light-heavy reduction with total reduction of 16mm at the position with the solid phase rate of 50-100%, wherein the total reduction of the first two rolls is 8mm, and the reduction of the third roll is 8mm; after the light and heavy reduction is carried out, the low-power shrinkage cavity of the casting blank can be controlled within 0.5 grade.
Example 2-example 3
The processes of example 2 and example 3 are the same as example 1, and the specific raw materials and process parameters are shown in tables 1 to 6.
Comparative example 1
5) Molten steel aluminum deoxidation treatment
Step 4), after the decarburization treatment of the molten steel is finished, continuously maintaining the vacuum degree of 103Pa at an RH station, adding 0.8kg/t of aluminum particles for deoxidation treatment, wherein the Si content of the deoxidized molten steel is 0.001%, the Al content is 0.008% and the [ O ] content is 84ppm; and (5) after the deoxidation is finished, continuously circulating for 10min, finishing the vacuum, and performing calcium treatment. And adding a low-carbon steel covering agent (the carbon content is less than or equal to 2%) on the surface of the molten steel after the calcium treatment is finished.
The other procedures are the same as in example 1.
Comparative example 2
5) Molten steel aluminum deoxidation treatment
Step 4), after the decarburization treatment of the molten steel is finished, continuously maintaining the vacuum degree of 103Pa at an RH station, adding 1.2kg/t of aluminum particles for deoxidation treatment, wherein the Si content, al content and [ O ] content of the molten steel are 0.001%, 0.011% and 20ppm respectively after the deoxidation treatment; and (5) after the deoxidation is finished, continuously circulating for 10min, finishing the vacuum treatment and performing calcium treatment. After the calcium treatment, a low-carbon steel covering agent (the carbon content is less than or equal to 2%) is added on the surface of the molten steel.
The other procedures are the same as in example 1.
Comparative example 3
6) Continuous casting of small square billets
Casting in a small square billet continuous casting machine with the section of 160mm multiplied by 160 mm; a low-carbon tundish covering agent (the carbon content is less than or equal to 2%) and ultra-low carbon protective slag (the carbon content is less than or equal to 8%) are used in the continuous casting process; the superheat degree of the molten steel is 32 ℃, the continuous casting drawing speed is 2.3m/min, and secondary cooling is carried out by adopting gas mist; the straightening temperature of the casting blank is 1150 ℃; after the casting blank is straightened, the casting blank is reduced by 1.0 grade in low power without adopting light and heavy reduction.
The other procedures are the same as in example 1.
The molten iron components, main parameters for desulfurization and demanganization, and the manganese and sulfur components of the pretreated molten iron of examples 1 to 3 are shown in table 1.
Table 1 examples molten iron pretreatment process parameters
From table 1, the embodiment adopts two-step desulfurization and demanganization pretreatment, and the Mn content of the molten iron can be reduced by 0.07-0.12%.
Examples 1 to 3 the oxygen supply time, oxygen supply amount and end point composition, temperature, and [ O ] content of the converter are shown in Table 2.
TABLE 2 example Process parameters of the converter
From Table 2, in the embodiment of pretreating molten iron by using demanganized molten iron, the converter end point can satisfy the conditions that the content of Mn is less than or equal to 0.05%, the content of P is less than or equal to 0.010%, and the content of S is less than or equal to 0.06%.
The energization time and refining completion components, temperatures, and [ O ] contents of refining in examples 1 to 3 are shown in Table 3.
TABLE 3 example refining Process parameters
As shown in Table 3, the refining was carried out by merely raising the temperature by energization without deoxidizing the slag and the molten steel, whereby the contents of the elements C, mn and P in the molten steel could be further reduced and the content of [ O ] could be increased by about 150ppm.
Examples 1 to 3 the RH cycle time, RH decarburization completion component, and [ O ] content are shown in Table 4.
TABLE 4 example RH decarburization Process parameters
As shown in Table 4, in the case of RH circulation for about 5min under the condition of no oxygen blowing and no more than 133Pa, C, O in the molten steel spontaneously carries out the carbon oxygen reaction of [ C ] + [ O ] = CO × (C ×) in the molten steel, the C content can be reduced to 0.002%, and the [ O ] content can be reduced to about 500 ppm.
The amount of the deoxidizer used after completion of RH decarburization, the oxygen content of molten steel after deoxidation, and chemical components in examples 1 to 3 and comparative examples are shown in Table 5.
TABLE 5 example and comparative example RH deoxygenation process parameters
From Table 5, in examples 1 to 3, high-purity ferrosilicon was used for deoxidation, and Al content in molten steel after deoxidation was controlled to be within 0.003% [ O ]]Is controlled within 50ppm, and Al is not generated because aluminum deoxidation is not adopted2O3The deoxidation product forms inclusions, and the molten steel does not need calcium treatment; comparative examples 1 to 3 were each aluminum grain-freeOxygen, 1.0kg/t of aluminum particles was added in comparative example 1, and the Al content of the molten steel reached 0.008% but [ O ]]The content still reaches 84ppm and exceeds T [ O ]]Less than or equal to 70 ppm; comparative example 2 adding 1.2kg/t aluminum pellets, molten Steel [ O ]]The content is reduced to 20ppm, but the Al content reaches 0.011 percent and exceeds the requirement that the Al content is less than or equal to 0.005 percent; comparative examples 1 to 2 the deoxidized product was Al2O3In order to ensure the castability of molten steel, calcium treatment is required.
Examples 1 to 3 the continuous casting process, the low power rating of the cast slab, and the like are shown in table 6 and fig. 1 to 4.
TABLE 6 continuous casting process parameters and strand low power for examples and comparative examples
From table 6 and fig. 1 to 4, comparative example 3 does not adopt light and heavy reduction, the casting blank has core cracks, and the shrinkage cavity reaches 1.0 grade; in the embodiments 1 to 3, after the light and heavy reduction (reduction of 16 mm) is adopted, the low-power quality of the casting blank is obviously improved, the shrinkage cavity is less than or equal to 0.5 grade, and no central crack exists.
Comparative example 4
1) KR pretreatment desulfurization of molten iron
The method comprises the steps of selecting molten iron containing 0.20% of Si, 0.33% of Mn, 0.107% of P and 0.030% of S for pretreatment, adding 7kg/t of high-quality active lime into a molten iron tank, stirring for 10min, carrying out desulfurization treatment, removing slag, and reducing the S content of the desulfurized molten iron to 0.001%.
The other procedures are the same as in example 1.
TABLE 7 consumption of auxiliary materials and Metal yields of converters in examples and comparative examples
From Table 7, the molten iron under the same conditions is adopted, and in the comparative example 4, only KR desulfurization pretreatment is carried out on the molten iron, so that the Mn content of the molten iron fed into the furnace is not reduced; in the embodiment 1, the molten iron is pretreated by two steps of KR desulfurization and demanganization, so that the Mn content of the molten iron fed into the converter can be effectively controlled to be less than or equal to 0.25 percent, the consumption of auxiliary materials of the converter is obviously reduced under the same operating conditions of full molten iron feeding and a double-slag method, and the metal yield is obviously increased.
Claims (8)
1. A preparation method of non-aluminum deoxidation raw material pure iron for an amorphous soft magnetic ribbon is characterized by comprising the following steps: KR pretreatment of molten iron, smelting in a converter, LF treatment, RH decarburization treatment, deoxidation treatment and continuous casting of small square billets; wherein, the KR pretreatment of the molten iron is carried out in two steps; firstly, adding high-quality active lime into a molten iron tank, stirring, performing desulfurization treatment, and removing slag; secondly, continuously adding iron scales into the molten iron tank, stirring, performing demanganization treatment, and removing slag; the converter adopts a double-slag method to smelt, demanganize and dephosphorize.
2. The method for preparing non-aluminum deoxidized raw material pure iron for the amorphous soft magnetic ribbon according to claim 1, which comprises the following steps:
1) Molten iron KR pretreatment desulfurization demanganization
Selecting molten iron with Si less than or equal to 0.40%, mn less than or equal to 0.40% and P less than or equal to 0.150% to carry out two-step KR pretreatment, wherein the S content and the Mn content of the molten iron are controlled within 0.002% and 0.25% respectively after desulfurization and demanganization;
2) Converter full molten iron charging double slag method for smelting demanganization and dephosphorization
Step 1), charging the molten iron into the molten iron, smelting and demanganizing and dephosphorizing by adopting a double slag method without charging scrap steel, controlling the end point temperature of the converter to be 1580-1620 ℃, and controlling the end point components: less than or equal to 0.06 percent of C, less than or equal to 0.05 percent of Mn, less than or equal to 0.010 percent of P, less than or equal to 0.006 percent of S, less than or equal to 0.002 percent of Ti, and the content of [ O ] in the molten steel is controlled between 500ppm and 800ppm; deoxidizing without adding a deoxidizing agent in the tapping process, and only adding high-quality active lime as top slag; in the later stage of tapping, slag blocking operation is carried out by adopting a slag blocking plug and a sliding plate for slag blocking, so that slagging and rephosphorization are avoided;
3) Refining without deoxidation treatment
Step 2) after the molten steel is refined, electrifying and heating the molten steel, further removing Mn, P and Ti in the molten steel, so that the refining end point Mn is less than or equal to 0.04 percent, P is less than or equal to 0.008 percent, ti is less than or equal to 0.001 percent, and the content of [ O ] in the molten steel is controlled between 600ppm and 900ppm;
4) RH circulation decarburization treatment
Step 3) after the molten steel reaches RH, circulating under the vacuum degree of less than or equal to 133Pa without oxygen blowing operation, and performing carbon-oxygen reaction on the original [ O ] and C element in the molten steel to perform decarburization treatment; the content of C in the recycled molten steel can be reduced to be within 0.002 percent, and the content of [ O ] in the molten steel is 400ppm to 600ppm;
5) Silicon deoxidation treatment of molten steel
After the decarburization treatment of the molten steel is finished, continuously keeping the vacuum degree of less than or equal to 133Pa at RH, adding high-purity silicon iron for deoxidation treatment, wherein the Si content of the molten steel is controlled to be 0.65-0.85%, the Al content is less than or equal to 0.003%, and the [ O ] content is less than or equal to 50ppm; continuing to circulate after the deoxidation is finished and then breaking the air; after the blank is broken, adding a low-carbon steel coating agent with the carbon content less than or equal to 2 percent;
6) Light and heavy reduction of continuous casting of small square billets
Casting in a small square billet continuous casting machine with the section of 160mm multiplied by 160 mm; in the continuous casting process, a low-carbon tundish covering agent with the carbon content of less than or equal to 2 percent and ultra-low-carbon covering slag with the carbon content of less than or equal to 8 percent are used; after straightening, carrying out three-roller light and heavy reduction with total reduction of 16mm at the position with solid fraction of 50-100%; after the light and heavy reduction is carried out, the low-power shrinkage cavity of the casting blank can be controlled within 0.5 grade.
3. The method for preparing non-aluminum deoxidized raw material pure iron for the amorphous soft magnetic ribbon as claimed in claim 1, characterized in that 6-9 kg/t of high quality active lime is added into a molten iron tank in the first step, wherein the CaO content of the high quality active lime is not less than 85%, the activity degree is not less than 260, and the mixture is stirred for 10-15 min; and secondly, continuously adding 8-15 kg/t of iron scale into the molten iron tank, and stirring for 15-20 min at the stirring speed of 40-60 r/min.
4. The method for preparing non-aluminum deoxidized raw material pure iron for the amorphous soft magnetic ribbon as claimed in claim 1, wherein the converter adopts a double-slag method for smelting, the adding amount of active lime is 38-48 kg/t, the adding amount of light-burned dolomite is 8-12 kg/t, the adding amount of raw dolomite is 10-20 kg/t, the adding amount of ore is 20-30 kg/t, the oxygen supply time is 15-18 min, and the oxygen supply amount is 7000m3～9000m3。
5. The method for preparing non-aluminum deoxidized raw material pure iron for the amorphous soft magnetic ribbon according to claim 2, wherein the energization heating treatment in the step 3) is performed for 30 to 40min, and the refining is finished when the temperature of molten steel reaches 1650 ℃ or higher.
6. The method for preparing non-aluminum deoxidized raw material pure iron for the amorphous soft magnetic ribbon as set forth in claim 2, wherein the addition amount of the high-purity silicon iron in the step 5) is 10 to 15kg/t, and the contents of elements P, S, al and Ti of the high-purity silicon iron do not exceed 0.02%.
7. The method for preparing non-aluminum deoxidized raw material pure iron for the amorphous soft magnetic ribbon as claimed in claim 2, wherein in the step 6), the superheat degree of molten steel in the continuous casting process is 30-45 ℃, the continuous casting drawing speed is 2.0-2.3 m/min, and secondary cooling is performed by adopting gas mist; the straightening temperature of the casting blank is 1000-1200 ℃.
8. The non-aluminum deoxidation raw material pure iron for the amorphous soft magnetic ribbon is characterized by comprising the following components in percentage by mass: c: less than or equal to 0.005%, si: less than or equal to 1.0 percent, mn: less than or equal to 0.06%, P: less than or equal to 0.015%, S: less than or equal to 0.010 percent, less than or equal to 0.005 percent of Al, less than or equal to 0.004 percent of Ti, less than or equal to 0.004 percent of N, less than or equal to 0.007 percent of T [ O ], and the balance of Fe and inevitable impurities.
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